Process of treating hydrocarbon gases and product thereof



Patented Aug. 3, 1926.

UNITED STATES 1,594,823 PATENT OFFICE.

GARLETON ELLIS, F MONTCLAIR, NEW JERSEY, ASSIGNOR 'IO BETH B. HUNT.

TRUSTEE. OF MOUNT'KISCO. NEW YORK.

PROCESS O! TREATING HYDROOARBON GASES AND PRODUCT THEREOF- ll'o Drawing.

The present application is a continuation in part of my on ending application Serial No. 206.052, filed lay th, 1919, Patent N 0. 1,412,233, and relates to treatment of hydrocarbon gases containing olefines with sub furic acid under conditions for producing from the olefines of the gases reactive acid liquor adapted for the replacement of the combined sulfuric acid radical with other groups or radicals to yield alcohols and other products of value.

According to the present invention hydrocarbon gases, that is to say hydrocarbons which are in the gaseous state at ordinary pressures and temperatures, such as natural gas or casing hea gas, are cracked to yield substantial proportions of olefines and treated with sulfuric acid to produce such reactive acid liquor.

As has been shown in contemporaneous applications. olofines, such as are present in cracked gasoline or in the gases resulting from the cracking of oils to produce gasoline. may be dissolved in or united with sulfuric acid of a suitable strength, and under certain conditions of temperature to form alkyl sulfuric acids which on hydrolysis by heating with water or treatment with steam give alcohols in a large measure corresponding to the olefincsfrom which the product was derived. For example, the ordinary still gases from a cracking plant may be treated with sulfuric acid of 1.8 specific gravity. and at a temperature preferably around 0.. to yield an extract that on hydrolysis afl'ords a mixture of so- Drop '1 alcohol and other alcohols including buty amyl and the like, but with isopropyl alcohol predominating in amount.

In a similar manner ketones may be obtained advantageously from the secondary alcohols produced as above or by direct oxidation of olefines of a suitable character.

The ketones contained. in a general manner, correspond with the alcohol or olefine from which they are derived. Thus from isopronyl alcohol by oxidation with chromic acid or by electrolytic or catalytic oxidation acetone may be obtained; one manner of acromplishing this is to pass isopropyl alcohol admixed with air through a mass of glowing copper or brass gauze whereby the alrohnl is largely oxidized to the corresponding kctone. namely acetone. In like manner Application llled February 7, 1822. Serial No. 584,784.

methyl ethyl kctone, diethyl ketone and higher ketones may be obtained.

The ethylene which is almost always present in gases of the character described above may be collected in sulfuric acid in the same manner as the hi her olefines, but in this case stronger acid an a higher temperature is usually used, although not always necessary. The strength of acid should be adjusted with respect to the temperature to secure a high degree of absorption. As propylene and the ighcr olefines are polymerized by hot sulfuric acid or acid that is too strong, the absorption of ethylene preferably should take place separately and subsequent to the absorption of all the other olefines. By hydrolysis of the ethylene extract ethyl alcohol is obtained.

The absorption of the olefines in sulfuric acid is facilitated by the presence of a considerable amount of heavy oil and preferably several volumes of heavy petroleum oil are employed to one volume of sulfuric acid. The gases may be bubbled through this mixture under proper conditions of temperature, refrigeration being resorted to when necessar With regard to the gases which may be employed, a considerable degree of latitude is possible. The gases useful for the purose include those derived by cracking ea'vy asphaltic oils in so-called coking stills, from high pressure stills, such as Burton stills operating on gas oil or fuel oil or other oils, various other types of stills working at atmospheric pressure or below atmospheric pressure, and from tube cracking apparatus into which the heavy oil with or without water or with a small amount of air, is injected and caused to pass through a cracking tube. Other gases. such as various modifications of oil gas. including pintsch gas. blau gas and the like may be used, and the invention claimed herein is concerned more as ecially with cracked gases, that is to say, t l9 product of cracking operations carried out on hydro carbons which are in the gaseous state at ordlnary pressures and temperatures prior to being subjected to cracking.

Tho gases used for cracking may be of various kinds. Gases which have been passed under sulphuric acid may be passed through a cracking zone to furnish more unsaturated material. The heating may be carried out under dehydrogenatin conditions to facilitate the yield of ol nes. If the cracking is carried out under diminishcd atmospheric pressure, an improved yield of olefines is obtained, and such procedure constitutes a preferred step of the present invention, but where for other reasons pressure mustbc employed, it is often desirable to use a catalytic material such as nickel orcopper,in theopcratlon. Dchydrogcuation is carried out advantageously with a nickel, copper or brass cata year. In a similar manner, natural gas or casing head gas and the like may be cracked to produce nnsaturated material. Preferably diminished pressure is employed and preferably also a catalyst such as nickel. For oxen 1g: casing head gas ma be over Ill l at a tem ature of wccn 500 and 700 0., and un er a pressure of l to 8 pounds below atmospheric to yield a mixture of ethylene, propylene and the like, which may be duly converted into alcohols or lrctoucc and these em loyed in fuel mixtures or for other uses in t 0 arts.

When casing head gasoline made from natural gas is used as a source of.ol those fractions boiling between 30 and 55 0., may be used and prefcrablythe lower boiling point from this out g ving a gas or vapor which may consist principally of pentane. In cracking these gases, the rate of flow through the cracking zone should be relatively slow, for instance, in tube cracking, from 8 to 40 cubic feet per hour of gas to each square inch of cross-sectional area of the cracking tube. At a higher rate of flow. a considerable amount of uncracked material would pass through. At a crackin temperature of 620 0., a yield was obtained in one case of about 18% of olefines higher than ethylene and about 5% ethylene. At a somewhat higher temperature hizhcr olefine yields are obtained. At a cracking temperature of about 720 (3., for example, a. yield was obtained of about 23.2% of olefines higher than ethylene and about 9.6% of ethylene. The olefincs higher than ethylene, which were determined by distillation of the olefine, dibromides to be mainly propvlene. are available for absorption in cold sulfuric acid to produce acid extract suitable for hydrolysis to the corresponding alcohols, principally isopropyl alcohol.

The cracked gases obtained as above and containing about 23.2% of such available olcfines in admixture with saturated hydrocarbons were passed through a series of four absorbers containing aqueous sulfuric acid of about 1.8 specific gravity, the tcmperature being maintained under C., or at a out ]5-20 C. Tl'lP acid extract obtained. which was practically free from tars and polymer bodies, was diluted with water and distilled, and gran distillation a large proportion of 0] ms was generated, which may be saved for reabsorption. The yield of alcohol was at the rate of about 1.2 liters per 1000 cubic feet of scans mixtum treated, but increased yields can, of course, be secured, particularly where pro vision is made to save the regenerated olefines. The alcohol obtained was of good odor and was about water soluble.

In producing acid extract it is desirable to pass the gases into sulfuric acid until the specific gravity falls from say 1.8 or 1.85 specific gravity to 1.3 or 1.4. Ordinarily the gas is assad in a rapid stream into the mixture 0 acid or mixture of acid and oil so as to keep the liquid violently agitated but not so violently as to cause heavy foami and priming. t the container in which 0 acid is being treated with the gas is about twice the capacity or of such size that the mixture of acid and oil fills it only half or two-thirds, than the may be passed thro at a rate as to cause a foam wh ch rises nearly .to the top of the container. Ordinarily by such rate es, of How of the gas with a gaseous mixture carrying 6 to 10% of unsaturated bodies a period of 8 hours will be aired to redues the specific gravity as in icalpd. 0n the other hand, due to' the presence of moisture in the gas the specific gravity of the acid may fall through abso tion of water and misleading results wil be obtained. When hydrogen sulphide is presout in the gas it also reacts, tending to weaken the acid and reduce the specific gravity. For these and other reasons the protracted action of the gas on the acid is undesirable and generally speaking 8 to 10 hours is sutlicient, giving a good extract and high yield of alcohol, while passage of the same gas for 24 or 48 hours through the acid of like strength might yield a product which on hydrolysis contained little or no alcohol. The treatment of the acid with gas between limiting periods of time as well as limiting ranges of temperatures and with acids of predetermined strength also forms a feature of the present invention.

Further with reference to the absorption of gases containing unsaturated material in sulfuric acid. it should be added that preferably as stated, the gas is passed through acid of the desired strength as, for example, 1.8 specific gravity until the spe cific gravity has been reduced to 1.3 or 1.4 bearing in mind that the extract may be given a fictitious reduction of gravity by absorption of water from the gas and also that the acid extract is liable to be weal:- ened by polymerization and through other reactions by protracted passage of the gas therethrough. Hence, it is desirableand in fact important to watch the progress of absorption introducing the gases as rapidly as the sulfuric acid or miir u I acid and oil will take up the unsaturated material, but without such an excessiize flow of as that the mixture primes and is carried out of the apparatus by foaming or entrainment to a considerable d ac, and in continuing such treatment unti the maximum amount of alkyl sulfuric acid is formed. At this point the operation should be sto pod and t 1e extract preferably run imme iatcly into water or otherwise diluted in order to effect hydrolizat-ion. Or if esters such as the acetate formats and the like are to be prepared the extract be treated with the salt of an organic ac:

I claim:

20 v 1. In the production of alcohols, the steps which consist in passing casing head as or natural gas through a heated zone on er a pressure subatmospheric to form oleflnes and in passing the gases thus produced into sulfuric acid under sulfat-ing conditions whereby an extract is obtained which on hydrolysis yields alcoholic bodies.

2. A fuel prepared by crackin natural gas, absorbing the uusaturate bodies formed in sulfuric acid under sulfating conditions and hydrolyzing the acid material obtained.

3. In the manufacture of acid extract suited for the production of alcohols on hydrolysis, the'step which consists in passing cracked gases containing unsaturated com onents through sulfuric acid under sulfating conditions a such a speed that vigorous agi tation takes place without excessive foamin and priming and in stopping the passage 0 the use when the content of alkyl sulfuric acid is at a maximum.

4. The process of making reactive acid liquor suited to the production of alcohols on hydrolysis. which comprises cracking gaseous hydro arhon material and extracting olefines therefrom with sulfuric acid of sufii 'cient strength to form sulfated derivatives of the olefines higher than ethylene at a temperature adjusted to the strength of the acid to avoid undue formation of polymers of such nlefines.

5. The process of making reactive acid liquor suited for the production of alcohols on hydrolysis. which comprises cracking natural as and extraction olefines therefrom with sulfuric acid of sufficient strength to form sulfatcd derivatives of the olefinea hicher than ethylene and at a temperature adiusted to the strength of the acid to avoid undue formation of polvmers of olcfines.

6. The process of making reactive liquor suited for the producti n of alcohols upon hvdr lvsis. which comprises cracking natural gas and extracting olcfines therefrom with re of sulfuric sulfuric acid until the specific vity falls frou tabout 1.85 to about 1.4 ofifl speed 0 gram 7. he process of producing from natural gas reactive acid extract suited for the Kro- I0 notion of alcohols on hydrol s, 1! 'ch comcgriscs cracking the s and 'ng the era ed gas with sulfuric acid, the ellcctive strength of which is below that of aqueous sulfuric acid of 1.85 specific gravity, and II which is of suflicient strength to be adapted for sultaticn of the olefines, and continuing. such treatment to the production of reactive acid liquor of specific gravity of 1.4 or 1.8.

e process of making reactive acid liquor suited for the production of alcohols on hydrolysis, which consists in cracking natural gas to produce olefines, extractin the propylene and higher olefines with furic acid of a strength equivalent to that u of aqueous sulfuric acid of about 1.8 specific gravity, under temperature conditions to avoid undue polymerization of olefines, and in further extracting the ethylene from such cracked gases separately with higher temperatures and stronger acid, and continuing the extraction to the production of an acid extiazt of a specific gravity of about 1.8 or i 9. The process of making reactive acid liquor, which consists in cracking natural gas to produce olefines, extracting the olefiues higher than ethylene with sulfuric acid of a strength equivalent to that of aqueous sulfuric acid of about 1.8 specific gravity, while maintaining the temperature under about 80 (3., and continuing such treatment to the production of reactive acid liquor of about 1.4 to 1.3 specific gravity 10. Reactive acid liquor of specific gravity about 1.3 or 1.4, consisting of the product of extraction treatment. while cooling, of cracked natural gas with sulfuric acid under sulfatinz conditions. said reactive acid liquor containing principally sulfated derivatives of olefinas of cracked naturalgas extracted therefrom by the sulfuric acid and present in quantity suflicient to bring the specific gravity from about 1.85 or 1.8 down to about 1.4-4.3.

11. The process of making reactive acid liquor in the production of alcohol bodies, which consists in selecting and cracking low boiling point fractions of easing head gas or natural gas at a tcmnerature of approximatelv 720 C., to produ e olefines. and extracting the propvlene and higher olefines under sulfatinz conditions with sulfuric acid of sufl'lcient stren th and under temperature condit ons to avoid undue oolymerization.

12. The process of making reactive acid lionor in the production of isonropyl and other alcoho s bv hydrolysis. which consists in s lecting hvdrocarbon components of casing head gas or natural gas boiling from 30" Ill to 55 0., tracking the hydrocarbons to prodncc olefines, and finally extractin the olefim-s higher than eth lane with sul uric acid under sulfating con itions and at a rats to I avoid undue polymerization.

13. In the pro uction of alcohols, the steps which consist in passing natnral gas hydrocarbons through a heated zone under a pressure sub-atmospheric to form 01 passing the gases thus produced acid under sulfntin conditions extract is obtaineg yields alcoholic bodies.

cfines and in into sulfuric whereb an which on hydro ysis CARLETON ELLIS.

to 55 (5., cracking the hydrocarbons to pro- (lure olcfincs, and finally extracting the olefincs higher than ethylene with sulfuric acid under sulfating conditions and at a rate to 6 avoid undue polymerization.

13. In the production of alcohols, the steps which consist in passing natural gas hydrocarbons through a heated zone under a pressure sub-atmospheric to form olefines and in passing the gases thus produced into sulfuric acid under sulfating conditions whereby an extract is obtained which on hydrolysis yields alcoholic bodies.

(JARLEToN ELLIS.

Certificate of Correction.

It is hereby certified that in Letters Patent No. 1,594,823, granted August 3. 1926, upon the application of Carleton Ellis, of Montclair, New Jersey, tor an iinproi ement in Processes of Treating Hydrocarbon Gases and Products Thereot, an error appears in the printed specification requiring correction as follows: Page 3, line (52, claim 6, after the Word reactive insert the word need; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent ()fiice.

Signed-and sealed this 28th day of September, A. D. 1926.

[smn] M. J. MOORE,

Acting Commissioner of Patents.

Certificate of Correction.

It is hereby certified that in Letters Patent No. 1,594,823, granted August 3 1926, upon the agplication of Carleton Ellis, of Montclair, New Jerse for an imprm ement in recesses of Treating Hydrocarbon Gases and Pro ucts Thereof, an error appears in the printed s cification requirin correction as follows: Puge 3, line 62, claim 6, after the W0 reactive insert 1; e word acid and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

Signed-and sealed this 28th day of September, A. D. 1926.

[SEAL] M J- Acti/ng Commissioner of Patents. 

